EP4359461A1 - Compositions de revêtement et revêtements pouvant être obtenus à partir de celles-ci ayant des résistances à la salissure et propriétés de nettoyage ou d'auto-nettoyage améliorées - Google Patents

Compositions de revêtement et revêtements pouvant être obtenus à partir de celles-ci ayant des résistances à la salissure et propriétés de nettoyage ou d'auto-nettoyage améliorées

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Publication number
EP4359461A1
EP4359461A1 EP22735150.9A EP22735150A EP4359461A1 EP 4359461 A1 EP4359461 A1 EP 4359461A1 EP 22735150 A EP22735150 A EP 22735150A EP 4359461 A1 EP4359461 A1 EP 4359461A1
Authority
EP
European Patent Office
Prior art keywords
component
group
linear
isocyanate
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22735150.9A
Other languages
German (de)
English (en)
Inventor
Yvonne REIMANN
Tanja Hebestreit
Jan Weikard
Hans-Josef Laas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4359461A1 publication Critical patent/EP4359461A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the invention relates to non-aqueous coating compositions containing at least one thioallophanate with free or blocked isocyanate groups and with silane groups, at least one isocyanate-reactive compound, at least one catalyst for crosslinking the silane groups and at least one alkoxysilyl-functional and/or hydroxyl-containing siloxane, the use of these coating compositions for the production of coatings and paintwork, in particular for use in the transport sector, i.e. in vehicles, in particular in ships, aircraft, motor vehicles such as cars, trucks, buses, large vehicles, rail vehicles, etc.
  • the coating compositions are particularly suitable for the production of clear lacquers.
  • 2K-PUR two-component polyurethane
  • the coating compositions should meet the requirements customarily made of the clearcoat film in paint finishes in the transportation sector, such as automotive OEM finishes and automotive refinish finishes.
  • WO2017/202692 discloses coating compositions and coatings obtainable therefrom which have improved soiling resistance and (self)cleaning properties and which are obtainable using aminosilane-functionalized isocyanates in combination with alkoxysilyl-functional siloxanes.
  • the use of thioallophanates containing silane groups and isocyanate groups in combination with alkoxysilyl-functional and/or hydroxyl-containing siloxanes is not mentioned or suggested.
  • the present invention relates to non-aqueous coating compositions containing or consisting of A) at least one polyisocyanate component (A) containing at least one silane-containing thioallophanate of the general formula (I) contains, in which
  • R 1 , R 2 and R 3 are identical or different radicals and each represent a saturated or unsaturated, linear or branched, aliphatic or cyclo-aliphatic or an optionally substituted aromatic or araliphatic radical having up to 18 carbon atoms, which may be up to 3 heteroatoms from the series oxygen, sulfur, nitrogen may contain,
  • X is a linear or branched organic radical with at least 2
  • Y is a linear or branched, aliphatic or cycloaliphatic, an araliphatic or aromatic radical with up to 18 carbon atoms and n is an integer from 1 to 20,
  • R 5 , R 6 , R 8 and R 9 are independently linear or branched alkyl groups having 1 to 4 carbon atoms,
  • R 15 , R 16 and R 17 are independently linear or branched alkyl groups having 1 to 4 carbon atoms
  • R 14 and R 18 are independently a group -L'-R 19 wherein
  • the invention also relates to the use of these nonaqueous coating compositions for the production of polyurethane coatings, in particular for use in the transport sector, i.e. for coating vehicles, in particular ships, airplanes, motor vehicles such as cars, trucks, buses, large vehicles, rail vehicles.
  • the lacquers are clear lacquers.
  • the coating composition according to the invention is non-aqueous.
  • the coating compositions contain organic solvents or are formulated as water-free systems.
  • the coating composition contains only minor amounts of water, preferably no water (anhydrous). Particular preference is given to containing less than 5% by weight of water, preferably less than 2.5% by weight of water, based on the total weight of the coating composition.
  • the polyisocyanate component (A) of the coating composition according to the invention contains at least one silane-containing thioallophanate of the general formula (I) in which
  • R 1 , R 2 and R 3 are identical or different radicals and each represent a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted aromatic or araliphatic radical with up to 18 carbon atoms, which optionally has up to 3 heteroatoms from the series may contain oxygen, sulfur, nitrogen,
  • X is a linear or branched organic radical with at least 2 carbon atoms
  • Y is a linear or branched, aliphatic or cycloaliphatic, araliphatic or aromatic radical having up to 18 carbon atoms and n is an integer from 1 to 20.
  • Polyisocyanate component (A) of the coating compositions according to the invention composed of at least one thioallophanate containing silane groups of the general formula (I).
  • thioallophanates containing silane groups are prepared by reacting a) at least one monomeric diisocyanate of the general formula (IV)
  • OCN - Y - NCO (IV) in which Y is a linear or branched, aliphatic or cycloaliphatic, an araliphatic or aromatic radical having up to 18 carbon atoms, with b) mercaptosilanes of the general formula (V) R1
  • R 1 , R 2 , R 3 and X have the meaning given above, in an equivalent ratio of isocyanate groups to mercapto groups of from 2:1 to 40:1.
  • Any diisocyanates having aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups are suitable as starting compounds a) for preparing the thioallophanates containing silane groups.
  • Suitable diisocyanates are those of the general formula (IV)
  • OCN - Y - NCO in which Y is a linear or branched, aliphatic or cycloaliphatic radical having up to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an optionally substituted aromatic or araliphatic radical having up to 18 carbon atoms, preferably 5 to 18 carbon atoms, such as 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4-, 4-Trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4
  • Further suitable diisocyanates can also be found, for example, in Justus Liebigs Annalen der Chemie Volume 562 (1949), pages 75-136.
  • Diisocyanates of the general formula (IV) in which Y is a linear or branched, aliphatic or cycloaliphatic radical having 5 to 13 carbon atoms are particularly preferred as starting component a).
  • Very particularly preferred starting components a) for the process according to the invention are 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4'- and/or 4 ,4'-diisocyanatodicyclohexylmethane or any mixtures of these diisocyanates.
  • Starting components b) for preparing the thioallophanates containing silane groups are any mercaptosilanes of the general formula (V) in which
  • R 1 , R 2 and R 3 are identical or different radicals and each represent a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted aromatic or araliphatic radical with up to 18 carbon atoms, which optionally contains up to 3 heteroatoms of the series may contain oxygen, sulfur, nitrogen, and
  • X is a linear or branched organic radical having at least 2 carbon atoms.
  • Suitable mercaptosilanes b) are, for example, 2-mercaptoethyltrimethylsilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyl3-triethoxysilane mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane and/or 4-mercaptobutyltrimethoxysilane.
  • Preferred mercaptosilanes b) for preparing the silane-containing thioallophanates are those of the general formula (V), in which
  • R 1 , R 2 and R 3 are identical or different radicals and each a saturated, linear or branched, aliphatic or cycloaliphatic radical with up to 6 mean carbon atoms, which can optionally contain up to 3 oxygen atoms, and
  • X is a linear or branched alkylene radical having 2 to 10 carbon atoms.
  • Particularly preferred mercaptosilanes b) are those of the general formula (V), in which
  • R 1 , R 2 and R 3 are each alkyl of up to 6 carbon atoms and/or alkoxy containing up to 3 oxygen atoms, provided that at least one of R 1 , R 2 and R 3 is such an alkoxy group stands, and
  • X is a propylene radical (-CH2-CH2-CH2-).
  • Very particularly preferred mercaptosilanes b) are those of the general formula (V), in which
  • R 1 , R 2 and R 3 are the same or different groups and are each methyl, methoxy or ethoxy, with the proviso that at least one of R 1 , R 2 and R 3 is a methoxy or ethoxy group, and
  • X is a propylene radical (-CH2-CH2-CH2-).
  • the diisocyanates a) are reacted with the mercaptosilanes b) at temperatures of 20 to 200° C., preferably 40 to 160° C., while maintaining an equivalent ratio of isocyanate groups to mercapto groups of 2:1 to 40:1, preferably from 4:1 to 30:1, particularly preferably from 6:1 to 20:1, to give thioallophanates.
  • the reaction can be carried out uncatalyzed as a thermally induced allophanatization.
  • suitable catalysts are preferably used to accelerate the allophanatization reaction.
  • These are the customary known allophanatization catalysts, for example metal carboxylates, metal chelates or tertiary amines of the type described in GB-A0 994 890, alkylating agents of the type described in US Pat are described in ER-A0 000 194 by way of example.
  • Suitable allophanatization catalysts are in particular zinc compounds, such as. B. zinc (II) stearate, zinc (II) n-octanoate, zinc (II) 2-ethyl-1-hexanoate, zinc (II) naphthenate or zinc (II) acetylacetonate, tin compounds such as tin(II) n-octanoate, tin(II) 2-ethyl-l-hexanoate, tin(II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin diacetate, zirconium compounds, such as zirconium(IV) 2-ethyl-l-hexanoate, zirconium(IV) neodecanoate, zirconium
  • Suitable, albeit less preferred, catalysts for preparing the thioallophanates containing silane groups are also those compounds which, in addition to the allophanatization reaction, also catalyze the trimerization of isocyanate groups to form isocyanurate structures.
  • Such catalysts are described, for example, in ER-A0 649 866 page 4, line 7 to page 5, line 15.
  • Preferred catalysts for preparing the thioallophanates containing silane groups are zinc and/or zirconium compounds of the type mentioned above.
  • These catalysts are used in the preparation of the silane-containing thioallophanates, if at all, in an amount of 0.001 to 5% by weight, preferably 0.005 to 1% by weight, based on the total weight of the reactants a) and b) and can be added both before the start of the reaction and at any time during the reaction.
  • the preparation of the thioallophanates containing silane groups is preferably carried out in the absence of a solvent. If appropriate, however, suitable solvents which are inert towards the reactive groups of the starting components can also be used. Suitable solvents are, for example, the conventional paint solvents known per se, such as e.g.
  • the starting diisocyanate a) or a mixture of different starting diisocyanates a) optionally under an inert gas, such as nitrogen, and optionally in the presence of a suitable solvent of the type mentioned, at a temperature between 20 and Submitted at 100°C.
  • the mercaptosilane b) or a mixture of different mercaptosilanes is then added in the amount indicated above and the reaction temperature for the Thiourethanization adjusted to a temperature of from 30 to 120° C., preferably from 50 to 100° C., if appropriate by a suitable measure (heating or cooling).
  • the thioallophanation can be started, for example without adding a catalyst, by heating the reaction mixture to a temperature of 120.degree. to 200.degree.
  • suitable catalysts of the abovementioned type are preferably used to accelerate the thioallophanation reaction, temperatures in the range from 60 to 140° C., preferably 70 to 120° C., being sufficient for carrying out the reaction, depending on the type and amount of catalyst used.
  • the catalyst which may also be used is admixed either to the diisocyanate component a) and/or to the silane component b) before the start of the actual reaction.
  • the intermediate thiourethane groups react spontaneously to form the desired thioallophanate structure.
  • the starting diisocyanates a), optionally containing the catalyst are optionally reacted under an inert gas, such as nitrogen, for example, and optionally in the presence of a suitable solvent of the type mentioned, generally at temperatures in the range from 60 to 140° which are optimum for the thioallophanation ° C, preferably 70 to 120 ° C, and reacted with the silane component b) optionally containing the catalyst.
  • an inert gas such as nitrogen, for example
  • a temperature in the range from 30 to 120° C., preferably from 50 to 100° C. is generally set for the pure thiourethanization reaction which takes place before the addition of the catalyst.
  • the thioallophantization reaction is carried out at temperatures of from 60 to 140.degree. C., preferably from 70 to 120.degree.
  • the course of the reaction can be changed by z. B. titrimetric determination of the NCO content.
  • the degree of thioallophanation ie the percentage of thiourethane groups which are converted to thioallophanate groups and form intermediately from the mercapto groups of component b) and can be calculated from the NCO content
  • the reaction is terminated. In the case of a purely thermal reaction, this can be done, for example, by cooling the reaction mixture to room temperature.
  • suitable catalyst poisons for example acid chlorides such as benzoyl chloride or isophthaloyl dichloride.
  • the reaction mixture is then preferably distilled by thin-layer distillation under high vacuum, for example at a pressure of less than 1.0 mbar, preferably less than 0.5 mbar, particularly preferably less than 0.2 mbar, under the most gentle conditions possible, for example at a temperature of 100 to 200° C, preferably from 120 to 180° C., freed from volatile constituents (excess monomeric diisocyanates, any solvents used and, if no catalyst poison is used, any active catalyst).
  • the resulting distillates which contain, in addition to the unreacted monomeric starting diisocyanates, any solvents used if a catalyst poison is not used, and an active catalyst, can be used without problems for renewed oligomerization.
  • the volatile constituents mentioned are removed from the oligomerization product by extraction with suitable solvents which are inert towards isocyanate groups, for example aliphatic or cycloabhatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
  • suitable solvents which are inert towards isocyanate groups, for example aliphatic or cycloabhatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
  • the products obtained are clear, practically colorless thioallophanate polyisocyanates, which generally have color numbers of less than 120 APHA, preferably less than 80 APHA, particularly preferably less than 60 APHA, and an NCO content of 2.0 to 18 .0% by weight, preferably 7.0 to 17.0% by weight, particularly preferably 10.0 to 16.0% by weight.
  • the average NCO functionality is generally from 1.8 to 3.0, preferably from 1.8 to 2.5, particularly preferably from 1.9 to 2.1.
  • the polyisocyanate component (A) may also contain other polyisocyanates having aliphatically, cycloaliphatically, araliphatically and/or aromatically attached isocyanate groups, which may also already contain silane groups.
  • These other polyisocyanates are, in particular, the known paint polyisocyanates with a uretdione, isocyanurate, iminooxadiazinedione, urethane, allophanate, biuret and/or oxadiazinetrione structure, as exemplified in Laas et al., J. Prakt. Chem.
  • Preferred other polyisocyanates which may be present in the polyisocyanate component (A) in addition to the thioallophanates containing silane groups are those of the type mentioned with exclusively aliphatically and/or cycloaliphatically bound isocyanate groups, in particular those based on PDI, HDI and/or IPDI.
  • these other polyisocyanates are present in the polyisocyanate component (A) in the coating compositions according to the invention in amounts of up to 70% by weight, preferably up to 60% by weight, particularly preferably up to 50% by weight, based on the Total amount of polyisocyanate component (A) consisting of at least one silane-containing thioallophanate and optionally other polyisocyanates.
  • the silane-containing thioallophanate polyisocyanates because of their very low viscosity, assume the role of a reactive diluent for the paint polyisocyanates, which are generally of higher viscosity.
  • Such blends of thioallophanate polyisocyanates containing silane groups with other polyisocyanates have the advantage of significantly higher isocyanate contents and functionalities with significantly lower viscosities compared to the previously known silane-functional polyisocyanates of the prior art with comparable silane contents.
  • the free isocyanate groups of the polyisocyanates of component (A) can also be used in blocked form. This is preferably the case when the coating materials according to the invention are used as one-component systems.
  • any blocking agent which can be used for blocking polyisocyanates and has a sufficiently low deblocking temperature can be used for the blocking.
  • blocking agents are well known to those skilled in the art. Examples of such blocking agents are described in EP 0626 888 A1 and EP 0 692 007 A1.
  • At least one compound is preferably selected as the blocking agent from the group consisting of alcohols, phenols, pyridinoes, thiophenols, quinolinoes, mercaptopyridines, quinolinols, amides, imides, imidazoles, imidazolines, lactams, oximes, pyrazoles, triazoles, malonic esters, acetoacetic esters, acetyl ketones and cyclopentanone -2-alkyl esters, used as a blocking agent.
  • the blocking is with a compound selected from the group consisting of mercaptopyridines, quinolinols, amides, imides, imidazoles, imidazolines, lactams, oximes, pyrazoles, triazoles, malonic esters, acetoacetic esters, acetyl ketones, and cyclopentanone-2-alkyl esters.
  • the coating compositions of the invention contain at least one isocyanate-reactive compound (B).
  • An “isocyanate-reactive compound” is a compound that carries at least one isocyanate-reactive group. Basically, mono- or polyhydric alcohols, Amino alcohols, amines and thiols are suitable as isocyanate-reactive compound B.
  • the aforementioned compounds have an average functionality of at least 2 isocyanate-reactive groups per molecule.
  • Suitable isocyanate-reactive compounds (B) are, for example, the usual at least difunctional polyhydroxy compounds known from polyurethane chemistry, such as. B. polyester polyols, polyether polyols, polycarbonate polyols and / or polyacrylate polyols, or any mixtures of such polyols.
  • Suitable polyester polyols (B) are, for example, those having an average molecular weight, which can be calculated from functionality and hydroxyl number, of from 200 to 3000, preferably from 250 to 2500, with a hydroxyl group content of from 1 to 21% by weight, preferably from 2 to 18% by weight.
  • an average molecular weight which can be calculated from functionality and hydroxyl number, of from 200 to 3000, preferably from 250 to 2500, with a hydroxyl group content of from 1 to 21% by weight, preferably from 2 to 18% by weight.
  • Polyhydric alcohols suitable for preparing these polyester polyols are, in particular, those with a molecular weight in the range from 62 to 400, e.g. B. 1,2-ethanediol, 1,2- and 1,3-propanediol, the isomeric butanediols, pentanediols, hexanediols, heptanediols and octanediols, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4, 4'-(l-Methylethylidene)-biscyclohexanol, 1,2,3-propanetriol, 1,1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-bis(hydroxymethyl )-1,3-propanediol or 1,3,5-tris(2-hydroxye
  • the acids or acid derivatives used to prepare the polyester polyols (B) can be aliphatic, cycloaliphatic and/or heteroaromatic in nature and, if appropriate, e.g. B. by halogen atoms, substituted and / or unsaturated.
  • suitable acids are, for example, polybasic carboxylic acids with a molecular weight in the range from 118 to 300 or derivatives thereof, such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic acid, maleic acid, maleic anhydride, dimeric and trimeric fatty acids, dimethyl terephthalate and bis-glycol terephthalate.
  • polybasic carboxylic acids with a molecular weight in the range from 118 to 300 or derivatives thereof, such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic acid, maleic acid, maleic anhydride, dimeric and trimeric fatty acids, dimethyl terephthalate and bis-glycol terephthalate.
  • Suitable polyester polyols (B) are also those as are known per se from lactones and simple polyhydric alcohols, such as. B. the ones mentioned above as examples, can be produced as starter molecules with ring opening.
  • suitable lactones for producing these polyester polyols are ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ - and ⁇ -valerolactone, ⁇ -caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone or any mixtures of such lactones.
  • lactone polyesters are generally prepared in the presence of catalysts, such as, for example, Lewis or Bronsted acids, organic tin compounds or titanium compounds, at temperatures of from 20.degree. to 200.degree. C., preferably from 50.degree. to 160.degree.
  • Suitable polyether polyols (B) are, for example, those having an average molecular weight, which can be calculated from functionality and hydroxyl number, of 200 to 6000, preferably 250 to 4000, with a hydroxyl group content of 0.6 to 34% by weight, preferably 1 to 27% by weight. %, as are accessible in a conventional manner by alkoxylation of suitable starter molecules.
  • Any desired polyhydric alcohols for example those with a molecular weight in the range from 62 to 400, as described above for the preparation of polyester polyols, can be used as starter molecules to prepare these polyether polyols.
  • Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any order or as a mixture in the alkoxylation reaction.
  • Suitable polyacrylate polyols (B) are, for example, those having an average molecular weight, which can be calculated from functionality and hydroxyl number or can be determined by gel permeation chromatography (GPC), from 800 to 50,000, preferably from 1000 to 20,000, with a hydroxyl group content of from 0.1 to 12% by weight, preferably 1 to 10, as can be prepared in a manner known per se by copolymerization of olefinically unsaturated monomers containing hydroxyl groups with olefinic monomers which are free of hydroxyl groups.
  • GPC gel permeation chromatography
  • Suitable monomers for preparing the polyacrylate polyols (B) are vinyl or vinylidene monomers such as styrene, ⁇ -methylstyrene, o- or p-chlorostyrene, o-, m- or p-methylstyrene, p-tert-butylstyrene, Acrylic acid, acrylonitrile, methacrylonitrile, acrylic and methacrylic acid esters of alcohols having up to 18 carbon atoms, such as. B.
  • vinyl or vinylidene monomers such as styrene, ⁇ -methylstyrene, o- or p-chlorostyrene, o-, m- or p-methylstyrene, p-tert-butylstyrene, Acrylic acid, acrylonitrile, methacrylonitrile, acrylic and methacrylic acid esters of alcohols having up to 18 carbon atoms, such as. B.
  • Preferred compounds (B) containing hydroxyl groups are polyester polyols, polycarbonate polyols and/or polyacrylate polyols of the type mentioned.
  • Particularly preferred compounds containing hydroxyl groups Compounds (B) are polyacrylate polyols of the type mentioned, which can optionally be used as a mixture with polyester polyols and/or polycarbonate polyols of the type mentioned. Very particular preference is given to using exclusively polyacrylate polyols of the type mentioned as the compounds containing hydroxyl groups.
  • amino-functional compounds can be used as further suitable isocanate-reactive compounds (B).
  • Preferred amines are organic, at least difunctional polyamines, preferably selected from the group consisting of 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, the isomer mixture of 2 ,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 4,4-diaminodicyclohexylmethane, hydrazine hydrate, dimethylethylenediamine, polyethers modified with amino end groups and compounds of the formula (VI) are used.
  • Z is a q-valent radical which is inert towards isocyanate groups, as defined by
  • Removal of the primary amino groups from an organic amine with a molecular weight in the range from 60 to 6000 having n primary aliphatically and/or cycloaliphatically bonded amino groups, which optionally has one or more heteroatoms and/or others that are reactive towards isocyanate groups and/or are inert at temperatures up to 100°C contains functional groups
  • R 20 and R 21 are identical or different organic radicals with 1 to 18 carbon atoms and q is an integer > 1.
  • amines are preferred which contain at least one amino group and at least one hydroxyl group (amino alcohols).
  • amino alcohols are preferably selected from the group consisting of diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexyl-aminopropane, 3-amino-1-methylaminobutane,
  • alkanolamines such as N-aminoethyl-ethanolamine, ethanolamine, 3-aminopropanol and neopentanolamine. It is of course also possible to use mixtures of the compounds bearing hydroxyl groups and amino groups described above as component B.
  • the coating compositions of the invention contain at least one alkoxysilyl-functional siloxane (Ci) and/or at least one hydroxyl-containing siloxane (Cii).
  • Siloxanes are known to those skilled in the art. These are components derived from pure silanes (that is, binary compounds consisting of Si and H) (derivatives of pure silanes) of the general formula RiSi-[0-SiR 2 ] n -0-SiR 3 , where R is a hydrogen atom or an alkyl group can.
  • the silicon atoms are linked to their neighboring silicon atom via exactly one oxygen atom, they contain at least one Si-O-Si bond. If at least one of the hydrogen atoms is replaced by an organic radical such as an alkyl group, these are also referred to as organosiloxanes.
  • Oligomeric or polymeric organosiloxanes (siloxanes with R ⁇ H) have long Si-O main chains and are in turn referred to as silicones.
  • organic radical of the organosiloxane also contains at least one hydroxyl group, ie if at least one hydrogen radical in the organic radical is substituted by a hydroxyl group, this is referred to in the present invention as a hydroxyl-containing siloxane (component Cii).
  • the organic radical of the organosiloxane described above also contains at least one alkoxysilyl group
  • at least one hydrogen group in the organic radical is substituted by an alkoxysilyl group, which means that at least a portion of a hydrogen in the derivative derived from the pure siloxane is substituted by an organic radical, which in turn has a contains an alkoxysilyl functional group, this is referred to in the context of the present invention as an alkoxysilyl functional siloxane (component Ci).
  • An alkoxysilyl functional radical is a functional group derived from an alkoxysilane, a moiety derived from a pure silane containing a Si-OR group. At least one hydrogen atom of a pure silane is therefore substituted by an alkoxy group —OR, ie an alkyl group connected to the silicon via oxygen. Examples which may be mentioned are mono-, di- or tri-methoxy- or -ethoxy-silane.
  • the alkoxysilyl-functional siloxanes (Ci) to be used according to the invention are derivatives of the siloxane in which at least one hydrogen atom has been substituted by an organic radical in which at least one hydrogen radical has in turn been replaced by an alkoxysilyl group.
  • the alkoxysilyl group is therefore always to be understood as a functional group of an alkyl group which is itself attached to the siloxane skeleton.
  • the alkoxysilyl group is always via a divalent organic radical R, for example Alkylene, linked to the Si-O-Si backbone and never directly attaches to the siloxane backbone of Si-O-Si units.
  • Preferred alkoxysilyl-functional siloxanes (Ci) can be described using the following general formulas (II):
  • R 5 , R 6 , R 8 and R 9 are independently linear or branched alkyl groups having 1 to 4 carbon atoms,
  • the siloxane (Ci) contains at least one —Si(R 12 ) z (OR 13 ) 3-z group.
  • the alkoxysilyl-functional siloxanes (Ci) can have a linear or branched form, depending on which radicals R 4 , R 7 and/or R 10 contain an alkoxysilyl group.
  • the siloxane is branched.
  • the siloxane is linear.
  • R 10 corresponds to a group -LR 11 in which L is an ethylene group and R 11 is a trialkoxysilane group and R 4 and R 7 are a group -LR 11 in which R 11 is one corresponds to hydrogen atom.
  • radicals R 5 , R 6 , R 8 , R 9 , R 12 and R 13 are particularly preferably identical or different alkyl radicals, and these radicals R 5 , R 6 , R 8 , R 9 , R 12 and R 13 are very particularly preferably linear alkyl groups having one to four carbon atoms, and the radicals R 5 , R 6 , R 8 , R 9 , R 12 and R 13 are again very particularly preferably methyl and/or ethyl radicals, in particular methyl radicals.
  • Component (Ci) contains at least one alkoxysilyl-functional siloxane. Accordingly, alkoxysilyl-functional siloxanes having the alkoxysilyl function in the side chain can be present alongside those in which the alkoxysilyl function(s) are terminal on the siloxane chain.
  • alkoxysilyl-functional siloxanes (Ci) are commercially available from Shin Etsu.
  • R 15 , R 16 and R 17 are independently linear or branched alkyl groups having 1 to 4 carbon atoms
  • R 14 and R 18 are independently a group -L'-R 19 wherein
  • radicals R 15 , R 16 and R 17 are particularly preferably identical or different alkyl radicals, these radicals R 15 , R 16 and R 17 are very particularly preferably linear alkyl groups having one to four carbon atoms, and the R 15 , R 16 and R 17 are methyl and/or ethyl radicals, especially methyl radicals.
  • R 14 and R 18 independently represent a group -L'-R 19 . That is, R 14 and R 18 can be the same or different radicals -L'-R 19 . If I are different radicals, the two radicals R 19 and / or the two radicals L 'can be different, with the requirement that at least one of the radicals R 14 or R 18 corresponds to a radical -L'-OH, ie at least one of the two radicals R 19 is an OH group.
  • Both radicals R 14 and R 18 particularly preferably correspond to the radical --L'--OH. Very particularly preferably, both radicals R 14 and R 18 correspond to the radical -L'-OH and L' is the same in both radicals R 14 and R 18 .
  • Component (Cii) contains at least one hydroxyl-containing siloxane. Accordingly, mixtures of the hydroxyl-containing siloxanes described above can be present as component (Cii).
  • hydroxyl-containing siloxanes (Cii) are commercially available from Shin Etsu.
  • siloxanes of components Ci and Cii can also be present in a mixture with one another.
  • the coating compositions according to the invention preferably contain from 0.001 to 5% by weight, preferably from 0.005 to 3% by weight and particularly preferably from 0.01 to 2% by weight, of component C, with the weight % information in each case are based on the total amount of polyisocyanate component (A), isocyanate-reactive component (B) and siloxane component (C).
  • the coating compositions of the invention also contain at least one catalyst (D) for crosslinking silane groups.
  • D catalyst for crosslinking silane groups.
  • These are any compound capable of accelerating the hydrolysis and condensation of alkoxysilane groups or, preferably, thermally induced silane condensation.
  • Suitable catalysts (D) are, for example, acids, such as. B. organic carboxylic acids, sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, acetic acid, trifluoroacetic acid, phosphoric acid monoesters and phosphoric acid diesters, such as. B. dibutyl phosphate, phosphoric acid 2-ethylhexyl ester, phosphoric acid phenyl ester and phosphoric acid bis (2-ethylhexyl) ester, and phosphonic acid and diphosphonic acid, as z. B. are described in WO 2007/033786.
  • bases such as. B. the N-substituted amidines l,5-diazabicyclo[4.3.0]non-5-ene (DBN) and l,5-diazabicyclo[5.4.0]undec-7-ene (DBU), or also metal salts and metal chelates , such as B. tetraisopropyl titanate, tetrabutyl titanate, titanium (IV) acetylacetonate, aluminum tri-sec-butylate, aluminum acetylacetonate, aluminum triflate, tin triflate or zirconium ethyl acetoacetate, as z. B. are described in WO 2006/042658.
  • Suitable catalysts (D) are also phosphoric acid and phosphonic acid esters of the type mentioned above, which are present in the form blocked with amines, preferably with tertiary amines. Particularly preferred catalysts of this type are those which release the acidic phosphoric acid and phosphonic acid esters, which are actually the effective catalysts, in the curing temperature range of automotive topcoats and clearcoats, for example in the range from 100 to 150° C., with elimination of the blocking amine. Suitable amine-blocked phosphoric acid catalysts (D) are described, for example, in WO 2008/074489 and WO 2009/077180.
  • catalysts (D) are organic sulfonic acids of the type mentioned above, which are used in blocked form, for example in amine-neutralized form or as an adduct of epoxides, as described in DE 2356768 B1, and above 100° C. the catalytically active ones releasing sulfonic acids.
  • catalysts (D) suitable for crosslinking silane groups are also tetraalkylammonium carboxylates, such as, for example, B. tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate,
  • Tetramethylammonium benzoate Tetramethylammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate and/or tetrabutylammonium benzoate.
  • Catalysts (D) suitable for crosslinking silane groups are also quaternary ammonium and phosphonium polyfluorides, such as those described, for. B. from ER-A0798299, ER-A0 896009 and ER-A0962 455 as trimerization catalysts for isocyanate groups are known.
  • suitable catalysts (D) are also zinc-amidine complexes, which can be prepared by the process of WO 2014/016019 by reacting one or more zinc(II) biscarboxylates with amidines.
  • Preferred catalysts (D) for crosslinking silane groups are acidic phosphoric acid esters, phosphonic acid esters and sulfonic acids of the type mentioned, which may be present in blocked form with amines, and tetraalkylammonium carboxylates of the type mentioned.
  • Particularly preferred catalysts (D) are amine-blocked phosphoric acid esters and sulfonic acids and the tetraalkylammonium carboxylates mentioned.
  • Very particularly preferred catalysts (D) are phosphoric acid phenyl ester and phosphoric acid bis(2-ethylhexyl) ester blocked with amines, tetraethylammonium benzoate and tetrabutylammonium benzoate.
  • the coating compositions according to the invention may also contain urethanization catalysts which are customary in isocyanate chemistry and which promote the reaction of the isocyanate groups Accelerate component (A) with the hydroxyl groups of component (B), such as B. tert.
  • urethanization catalysts which are customary in isocyanate chemistry and which promote the reaction of the isocyanate groups Accelerate component (A) with the hydroxyl groups of component (B), such as B. tert.
  • Amines such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-endoethylenepiperazine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N-dimethylaminocyclohexane, N,N'-dimethylpiperazine or metal salts such as iron(III) chloride, zinc chloride, zinc 2-ethyl caproate, tin(II) octanoate, tin(II) ethyl caproate, dibutyltin(IV) dilaurate, zirconium(IV) isopropylate, zirconium(IV) n-butylate, zirconium(IV) 2-ethylhexanoate, zirconyl octanoate, bismuth(III) 2-ethylhexanoate, bismuth(III) octoate or molybdenum glycolate.
  • the catalysts (D) are present in the coating compositions according to the invention as an individual substance or in the form of any mixtures with one another in amounts of from 0.005% by weight to 5% by weight, preferably from 0.005% by weight to 2% by weight, especially preferably from 0.005% by weight to 1% by weight, calculated as the sum of all the catalysts (D) used and based on the total amount of polyisocyanate component (A), isocyanate-reactive component (B) and siloxane component (C).
  • the coating compositions of the invention may contain further auxiliaries and additives (E).
  • auxiliaries and additives known to those skilled in the art of coatings technology, such as e.g. B. solvents, UV stabilizers, antioxidants, water scavengers, leveling agents, rheology additives, slip additives, defoamers, fillers and / or pigments.
  • the coating compositions according to the invention can be diluted, for example, with customary organic solvents (ei).
  • Solvents suitable for this are, for example, the paint solvents already described above in the preparation of the silane groups containing silane groups as solvents that may be used as well, which are chemically inert towards the reactive groups of the coating composition components and have a water content of at most 1.0% by weight, particularly preferably at most 0.5% by weight based on the solvent used.
  • Suitable UV stabilizers (E2) can preferably be selected from the group consisting of piperidine derivatives, such as 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-1,2,2,6,6-pentamethylpiperidine , bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
  • Benzophenone derivatives such as 2,4-dihydroxy-, 2-hydroxy-4-methoxy-, 2-hydroxy-4-octoxy-, 2-hydroxy-4-dodecyloxy- or 2,2'-dihydroxy-4-dodecyloxy-benzophenone ;
  • Benztriazole derivatives such as 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2H -Benzotriazol- 2-yl)-4,6-bis( 1 -methyl- 1 -phenylethyl)
  • triazine derivatives such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2- [4-[(2-Hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; oxalanilides such as 2-ethyl-2'-ethoxy- or 4-methyl-4'-methoxyoxalanilide; salicylic acid esters such as phenyl salicylate, 4-tert-butylphenyl salicylate, 4-tert-octylphenyl salicylate; cinnamic acid ester derivatives such as methyl ⁇ -cyano- ⁇ -methyl-4-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-4-
  • one or more of the UV stabilizers (E2) mentioned by way of example are added to the coating composition according to the invention, preferably in amounts of 0.001 to 3.0% by weight, particularly preferably 0.01 to 2% by weight, calculated as the total amount of UV stabilizers used Stabilizers are added based on the total amount of polyisocyanate component (A), isocyanate-reactive component (B), component (E) and siloxane component (C).
  • Suitable antioxidants are preferably sterically hindered phenols, which can preferably be selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol (ionol), pentaerythritol-tetrakis(3-(3,5 -di-tert-butyl-4-hydroxy-phenyl)-propionate), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, triethylene glycol bis(3-tert-butyl -4-hydroxy-5-methylphenyl)propionate, 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,2'-thiodiethylbis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionate]. If required, these can be used individually or in any combination with one another.
  • antioxidants (E3) are preferably used in amounts of 0.01 to 3.0% by weight, particularly preferably 0.02 to 2.0% by weight, calculated as the total amount of antioxidants used, based on the total amount of polyisocyanate component (A ), isocyanate-reactive component (B) and siloxane component (C) are used.
  • water scavengers for example orthoameisenestem, such as. B. triethyl orthoformate, or vinylsilanes, such as. Example, vinyltrimethoxy silane.
  • water scavengers come, if at all, in amounts of 0.01% by weight up to 5% by weight, preferably from 0.01% by weight to 2% by weight, based on the total amount Polyisocyanate component (A), isocyanate-reactive component (B) and siloxane component (C) are used.
  • the coating compositions according to the invention can optionally contain suitable leveling agents (ES), for example organically modified siloxanes, such as e.g. B. polyether-modified siloxanes, polyacrylates and / or fluorosurfactants included.
  • suitable leveling agents for example organically modified siloxanes, such as e.g. B. polyether-modified siloxanes, polyacrylates and / or fluorosurfactants included.
  • These leveling agents come, if at all, in amounts of 0.01% by weight up to 3% by weight, preferably from 0.01% by weight up to 2% by weight, particularly preferably from 0.05 to 1 5% by weight, based on the total amount of polyisocyanate component (A), isocyanate-reactive component (B) and siloxane component (C).
  • the coating compositions of the invention may also contain melamines in minor amounts as further crosslinker components (Ee).
  • Suitable melamines include monomeric melamine, polymeric melamine-formaldehyde resin, or a combination thereof.
  • the monomeric melamines include low molecular weight melamines containing an average of three or more methylol groups etherified with a C1 to C5 monohydric alcohol such as methanol, n-butanol or isobutanol per triazine nucleus and an average degree of condensation up to about 2 and preferably in the range of from about 1.1 to about 1.8, and having a mononuclear species content of not less than about 50% by weight.
  • the polymeric melamines have an average degree of condensation greater than about 1.9.
  • suitable monomeric melamines include alkylated melamines such as methylated, butylated, isobutylated melamines, and mixtures thereof. Many of these suitable monomeric melamines are commercially supplied. For example, Cytec Industries Inc. of West Patterson, New Jersey supply Cymel 301 (degree of polymerization of 1.5, 95% methyl and 5% methylol), Cymel 350 (degree of polymerization of 1.6, 84% methyl and 16% methylol), 303, 325, 327, 370 and XW3106, all of which are monomeric melamines.
  • Suitable polymeric melamines include high amino melamine (partially alkylated, -N, -H) known as Resimene BMP5503 (molecular weight 690, polydispersity of 1.98, 56% butyl, 44% amino) available from Solutia Ine., St. Louis, Missouri, or Cymell 158 provided by Cytec Industries Inc. of West Patterson, New Jersey. Cytec Industries Inc. also supply Cymel 1130 at 80 percent solids (degree of polymerization of 2.5), Cymel 1133 (48% methyl, 4% methylol and 48% butyl), both of which are polymeric melamines.
  • auxiliaries and additives (E) in the coating compositions of the invention are known to the person skilled in the art and, if at all, are used in amounts customary in paint technology.
  • auxiliaries and additives can be found, for example, in Bodo Müller, "Additive compact”, Vincentz Network GmbH & Co KG (2009). Production of the coating agent and use
  • coating composition is a one-component (1K) coating composition
  • compounds (A) containing isocyanate groups are chosen whose free isocyanate groups are blocked with blocking agents. Blocking agents to be used or preferably to be used are described under the comments on component (A).
  • components (A), (B), (C), (D) and, if appropriate, (E) are intimately mixed in any order in succession or together, preferably using suitable mixing units, until a homogeneous solution is obtained.
  • the polyisocyanate component (A), which contains at least one silane-containing thioallophanate polyisocyanate, the isocyanate-reactive component (B) and, if present, the hydroxyl-containing siloxane(s) (Cii) are usually used in amounts such that each isocyanate group of the polyisocyanate component (A) 0.5 to 3.0, preferably 0.6 to 2.0, particularly preferably 0.8 to 1.6 isocyanate-reactive groups of the components (B) and (Cii) fall ent.
  • 2 coating composition components are produced separately, one of which contains the polyisocyanate component (A) and a second one the isocyanate-reactive component (B).
  • one of the two coating material components contains the siloxane component (C) or both coating material components contain a proportion of the siloxane component (C), one coating material component preferably containing component (C) alone.
  • the coating agent component containing component (B) also contains component (C).
  • the catalyst component (D) and any further auxiliaries and additives (E) to be used can be added to the coating composition component containing the polyisocyanate component (A) and/or the isocyanate-reactive component (B).
  • the 1K and 2K coating materials obtained in this way can be applied by methods known per se, for example by spraying, brushing, dipping, flow-coating or with the aid of rollers or doctor blades in one or more layers.
  • any substrates can be considered as substrates, e.g. B. metal, wood, glass, stone, ceramic materials, concrete, hard and flexible plastics, textiles, leather and paper, which can optionally also be provided with customary, known primers, surfacer coats, base coats and / or clear coats before coating.
  • the coating compositions of the invention are preferably used in areas of application in which high demands are made on a coating in terms of optical quality and resistance to mechanical scratching, and in which the coatings also have a high resistance to soiling and should be easy to clean. These include in particular decorative, protective and / or effect, highly scratch-resistant coatings and paints in the field of transport, such as vehicle bodies such as ships and airplanes, and motor vehicle bodies such. B. motorcycles, buses, trucks, cars or rail vehicles or parts thereof.
  • the coating compositions according to the invention are very particularly suitable for the production of coatings and finishes, in particular clear lacquers, in automotive refinishing and in automotive OEM finishing.
  • the coating compositions according to the invention are preferably also used in the clearcoat or topcoat of multilayer structures, especially in multi-stage coating processes in which first a pigmented basecoat layer and then a layer of the coating composition according to the invention are applied to an optionally precoated substrate.
  • a further embodiment of the present invention relates to a method for coating surfaces, containing the steps a) applying the coating composition to a substrate; and b) curing the coating agent.
  • the coating compositions according to the invention are preferably processed by spray application methods, such as compressed air spraying, airless spraying, high-speed rotation, electrostatic spray application (ESTA), optionally combined with hot spray application, such as hot-air hot spraying.
  • spray application methods such as compressed air spraying, airless spraying, high-speed rotation, electrostatic spray application (ESTA), optionally combined with hot spray application, such as hot-air hot spraying.
  • ESA electrostatic spray application
  • hot spray application such as hot-air hot spraying.
  • the mixing of the individual components of the coating compositions according to the invention preferably takes place immediately before processing and can advantageously take place in so-called 2-component systems.
  • the coating compositions according to the invention can be cured immediately after application or after a certain flash-off time has been observed.
  • the flash-off time is used, for example, for the leveling and degassing of the paint layers or for the evaporation of volatile components, such as e.g. B. Solvents.
  • the required duration of the flash-off time can be specifically controlled, for example, by using increased temperatures and/or by reducing the air humidity.
  • the final curing of the applied coating compositions according to the invention finally takes place according to customary and known methods, such as. B. heating in a convection oven, irradiation with IR lamps or near infrared (NIR radiation), preferably in a temperature range of 30 to 200 ° C, more preferably 40 to 190 ° C and very particularly preferably 50 to 180° C. for a period of 1 min to 12 h, particularly preferably 2 min to 6 h and very particularly preferably 3 min to 4 h.
  • NIR radiation near infrared
  • the method is preferably used for coating surfaces in the areas of application mentioned above.
  • the coatings produced in this way from the coating compositions of the invention, which are preferably clear lacquers, are notable for high scratch resistance and solvent resistance, as well as good soiling resistance and (self)cleaning properties.
  • the present invention relates to the use of the coating compositions according to the invention described above for the production of coatings and paint systems.
  • Said coatings and finishes are preferably used to produce clear coats.
  • compositions of the invention to produce coatings and finishes in automotive refinishing and in automotive OEM finishing.
  • a further embodiment of the present invention relates to substrates which are coated with one or more coating compositions according to the invention.
  • the substrate is preferably selected from the group consisting of metal, wood, wood materials, glass, stone, ceramic materials, mineral building materials, hard and flexible plastics, textiles, leather and paper.
  • the NCO content was determined titrimetrically according to DIN EN ISO 11909:2007-05.
  • the flow time was determined according to DIN EN ISO 2431:2012-03 using an ISO flow cup with a 5 mm nozzle.
  • the polyols described below were each mixed with a commercially available leveling additive (BYK 331; BYK-Chemie GmbH, Wesel, DE, used as a 50% solution in MPA), the light stabilizers Tinuvin 292 and Tinuvin 384-2 (BASF SE , Ludwigshafen, DE, use 1% or 1.5% delivery form on binder solid) as well as for all silane-containing formulation Vestanat EP-CAT 11 B (tetraethylammonium benzoate, 50% solution in butanol, Evonik, Essen, Germany, use 1 % based on solid binder) as catalyst C) and, depending on the formulation, the additives KF-6000 or KR-410 (Shin-Etsu, Japan) are homogeneously mixed by intensive stirring at room temperature.
  • BYK 331 BYK-Chemie GmbH, Wesel, DE, used as a 50% solution in MPA
  • the light stabilizers Tinuvin 292 and Tinuvin 384-2 BASF SE , Ludwig
  • Table 1 shows the compositions of the individual formulations.
  • the coating materials were each applied to glass plates using a gravity cup gun and, after 10 minutes flashing off at room temperature, within 30 minutes at 140°C hardened. All glass slides were stored at room temperature for at least 48 hours prior to testing.
  • the resistance to condensation water was tested according to DIN EN ISO 6270-2 CH:2018 for 240 hours.
  • the measurements of the contact angles with water were carried out both on glass and on the assembly (see below).
  • the measurements were carried out on an OCA20 device from Data Physics.
  • 10 drops each containing approx. 2 pL of distilled water were placed on the coating surface and the resulting contact angle was recorded after approx. 3 s.
  • the mean value was calculated from the 10 measured values.
  • the SCA software from Data Physics was used for droplet analysis and evaluation.
  • the scratch resistance of the easy-to-clean properties was tested by contact angle measurements before and after scratching on the complete OEM multi-layer structure on sheet steel.
  • the coating materials were applied using a gravity cup gun as clear coats to KTL panels (dry layer thickness approx. 40 pm test panels from Daimler, Germany), which had previously been coated with a commercially available lK-OEM hydro-filler (dry layer thickness approx. 35 pm) and a black lK-OEM hydro-base coat (Dry layer thickness approx. 15 pm) had been coated. While the hydro-surfacer was fully cured by baking at 165°C for 20 minutes, the hydro-basecoat was only pre-dried for 10 minutes at 80°C. After the clear coats had been applied, the base coat layer and the clear coat layer were cured together at 140° C. within 30 minutes. All panels were stored at room temperature for at least 48 h before testing.
  • Table 2 shows the results of the performance tests in comparison, each determined after a storage time of at least 48 hours at 23°C. Production of the lK-OEM-Hydrobasecoat
  • Aliphatic polyisocyanurate polyisocyanate based on HDI (Covestro Deutschland AG, Leverkusen), 90% solution in n-butyl acetate/solvent naphtha 100 (1:1), NCO content: 19.6%, viscosity at 23° C.: 550 mPas.
  • Aliphatic polyisocyanurate polyisocyanate based on IPDI (Covestro Deutschland Ag, Leverkusen), 70% solution in 1-methylpropylacetate-2/xylene (1:1), NCO content: 11.9%, viscosity at 23° C.: 1500 mPas.
  • Silane functional polyisocyanate PI Silane functional polyisocyanate PI:
  • the catalyst was deactivated by adding 0.1 g of orthophosphoric acid and the unreacted monomeric HDI was separated off in a thin-film evaporator at a temperature of 130° C. and a pressure of 0.1 mbar. 486 g of a practically colorless, clear polyisocyanate mixture were obtained, which had the following characteristics and composition:
  • Polyacrylate polyol (Allnex Germany GmbH, Bitterfeld-Wolfen, DE), 65% solution in butyl acetate/xylene (75:25), OH number: 150 mg KOH/g (based on delivery form), viscosity at 23°C: approx. 2400 mPas.
  • KR-410 linear alkoxysilyl functional siloxane (Shin-Etsu, Japan), as supplied.
  • KF-6000 linear hydroxy-functional siloxane (Shin-Etsu, Japan), as supplied.
  • examples 4 to 7 according to the invention show better easy-to-clean properties in the marker test and consistently high contact angles when applied to glass. While comparative examples 1 and 3 are notable for their poor results in the marker test, comparative example 2 shows poorer values for solubility and at the same time a lower contact angle when applied to glass.
  • example 4 according to the invention with an alkoxysilsyl-functional additive shows a significantly higher contact angle when the clear lacquer is applied to glass.
  • the contact angle, measured on the structure, remains stable in inventive examples 4 with an alkoxysilyl-functional additive and 5 with a hydroxysilyl-functional additive even after wet scratching, whereas the contact angle of comparative examples 8 and 9 falls significantly after wet scratching.
  • the coating compositions of the invention can be used to obtain coatings which are at least comparable to prior art coatings in terms of their solvent resistance and have clear advantages over such coatings in terms of their scratch resistance and easy-to-clean properties.

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Abstract

L'invention se rapporte à des compositions de revêtement non aqueuses contenant au moins un thioallophanate ayant des groupes isocyanate libres ou bloqués et ayant des groupes silane, au moins un composé capable de réagir avec les isocyanates, au moins un catalyseur pour la réticulation des groupes silane et au moins un siloxane à fonctionnalité alcoxysilyle et/ou à teneur en groupe hydroxyle. L'invention se rapporte également à l'utilisation de ces compositions de revêtement pour la production de revêtements et de systèmes de peinture, en particulier destinés à être utilisés dans le secteur des transports, c'est-à-dire dans des véhicules, en particulier dans des navires, des avions, des véhicules à moteur tels que des voitures, des camions, des autobus, des véhicules de grande taille, des véhicules sur rails, etc. Les compositions de revêtement sont en particulier appropriées pour la production de vernis transparents.
EP22735150.9A 2021-06-21 2022-06-20 Compositions de revêtement et revêtements pouvant être obtenus à partir de celles-ci ayant des résistances à la salissure et propriétés de nettoyage ou d'auto-nettoyage améliorées Pending EP4359461A1 (fr)

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EP21180672.4A EP4108697A1 (fr) 2021-06-21 2021-06-21 Milieu de revêtement et revêtements pouvant être obtenu à partir de celui-ci à résistance à la salissure et à des propriétés (auto-)nettoyantes améliorées
PCT/EP2022/066712 WO2022268707A1 (fr) 2021-06-21 2022-06-20 Compositions de revêtement et revêtements pouvant être obtenus à partir de celles-ci ayant des résistances à la salissure et propriétés de nettoyage ou d'auto-nettoyage améliorées

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EP22735150.9A Pending EP4359461A1 (fr) 2021-06-21 2022-06-20 Compositions de revêtement et revêtements pouvant être obtenus à partir de celles-ci ayant des résistances à la salissure et propriétés de nettoyage ou d'auto-nettoyage améliorées

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CN117545788A (zh) 2024-02-09
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